Method of controlling insects and arachnids with tetrahydroquinoxalinyl phosphates or thiophosphates

ABSTRACT

A METHOD OF PROTECTING CROPS AND CONTROLLING INSECTS OR ARACHNIDS BY APPLYING A COMPOUND HAVING THE FORMULA:   2-(R1-P(=X)(-R2)-O-),R3-5,6,7,8-TETRAHYDROQUINOXALINE   WHEREIN X IS A MEMBER SELECTED FROM THE GROUP CONSISTING OF SULFUR AND OXYGEN; R1 AND R2 ARE EACH LOWER ALKYL, LOWER ALKOXY, LOWER THIOALKYL, PHENYL, HALOPHENYL, BENZYL OR -NR4R5; R3 IS HYDROGEN OR LOWER ALKYL; AND R4 AND R5 ARE EACH SELECTED FROM THE GROUP CONSISTING OF HYDROGEN AND LOWER ALKYL.

United States Patent Int. Cl. A01n 9/36 US. Cl. 424-200 10 Claims ABSTRACT OF THE DISCLOSURE A method of protecting crops and controlling insects or arachnids by applying a compound having the formula:

wherein X is a member selected from the group consisting of sulfur and oxygen; R and R are each lower alkyl, lorwer alkoxy, lower thioalkyl, phenyl, halophenyl, benzyl or -NR -R R is hydrogen or lower alkyl; and R and R are each selected from the group consisting of hydrogen and lower alkyl.

This application is a divisional of our copending application for Letters Patent, Ser. No. 658,637, filed Aug. 7, 1967, now Pat. -No. 3,505,327.

The present invention relates to new tetrahydroquinoxalinyl phosphates, thiophosphates and the like, a method for the preparation thereof, and to a method of controlling insects and arachnids therewith. More particularly, it is concerned with a compound of the formula:

r J N/ wherein X is a sulfur or an oxygen atom, R and R are each lower alkyl, lower alkoxy, lower thioalkyl, aryl, such 0,0-diethyl 0-5 ,6,7 ,8-tetrahydro-6 (7 -methy1-2-quinoxalinyl phosphorothioate,

ice

0,0-dimethyl O-5,6,7,8-tetrahydro-2-quinoxalinyl phosphorothioate,

0,0,-diisopropyl O-5,6,7,8-tetrahydro-2-quinoxalinyl phosphorothioate,

Diisopropyl 5,6,7,8-tetrahydro-2-quinoxalinyl phosphate,

0,0-diethyl 0-5,6,7,8-tetrahydro-Z-quinoxalinyl phosphorothioate,

O-ethyl O-methyl 0-5,6,7,8-tetrahydro-2-quinoxalinyl phosphorothioate,

N,N-dimethyl-O-ethyl 0-5,6,7,8-tetrahydro-2-quinoxalinyl phosphoroamidothioate,

O-ethyl 0-5 ,6,7,8-tetrahydro-6 (7) -methyl-2-quinoxalinyl phenylphosphonothioate,

O-S-dimethyl 0-5,6,7,8-tetrahydro-2-quinoxalinyl phosphorodithioate,

O-ethyl 0-5,6,7,S-tetrahydro-Z-quinoxalinyl ethanephosphonate,

S,S-dimethyl O-5,6,7,8-tetrahydro-Z-quinoxalinyl phosphorodithioate,

O-isopropyl O-methyl O-5,6,7,8-tetrahydro-2-quinoxalinyl phosphorothioate,

Diethyl 5,6,7,8-tetrahydro-Z-quinoxalinyl phosphate and 0,0-dipropyl O-5,6,7,8-tetrahydroquinoxalinyl phosphorothioate.

Th compounds of the invention can be synthesized in a straightforward and conomical manner by effecting a reaction between a tetrahydroquinoxaline and a phosphorus-containing ester halide in the presence of a strong base. The overall reaction may be graphically written as follows:

wherein Y is halogen, such as chlorine or bromine; X is sulfur or oxygen; R and R are each selected from the group consisting of lower alkyl, lower alkoxy, lower thioalkyl, NR R and aryl, such as phenyl or halophenyl, and alkaryl, such as benzyl; and R is hydrogen or lower alkyl; and R and R are each selected from the group consisting of hydrogen and lower alkyl. Preferably, the reaction is carried out in the presence of an inert solvent, such as t-butanol, dimethylsulfoxide, dimethylformamide or water over a wide-range of temperatures, usually between about 0" C. and C. Among the strong bases which are useful in the process are sodium and potassium t-butoxide, sodium and potassium hydroxide and tertiary amines, such as trimethylamine.

The tetrahydroquinoxalines can be conveniently prepared by initially halogentting a cyclohexanone. The reaction is carried out in the presence of an acid, such as glacial acetic acid, and the overall reaction is shown by the following graphic equation:

wherein X is either chlorine or bromine.

The halogenated cyclohexanone may then be treated with aqueous ferric chloride solution at an elevated temperature, preferably at boiling, to give a cyclohexanedione, which is next treated with a glycinamide hydrohalide, such as glycinamide hydrochloride, at from C. to 100 C. in the presence of a suitable base to yield the desired tetrahydroquinoxaline. The reaction is graphically illus trated as:

An illustrative tetrahydroquinoxaline reactant for Reaction [I] above is:

2-0xy-5,6,7,8-tetrahydro quinoxaline, 6 (7 -Methyl-2-oxy-5,6,7,S-tetrahydroquinoxaline, and 6 (7 -Ethyl-2-oxy-5, 6,7,8-tetrahydroquinox aline.

Exemplary phosphorylating agents which may be employed in Reaction [1] above are:

0,0-dimethyl pohsphorochloridothioate, 0,-O-diethyl phosphorochloridothioate,

O-methyl, O-ethyl phosphorochloridothioate, 0,0-diisopropyl phosphorobromidothioate, 0,0-di-n-butyl phosphorochloridothioate, 0,0-dimethyl phosphorochloridate,

0,0-diethyl phosphorochloridate,

O-ethyl ethanephosphonochloridothioate, O-ethyl-N,N-dimethyl phosphoramidochloridothioate, O-ethyl, phenylphosphonochloridothioate, O-ethy1-N-isopropyl phosphoramidochloridothioate, O-ethyl-N-methyl phosphoramidochloridothioate, Diethylphosphorochloridotrithioate, and Diethylphosphinothioyl bromide.

The compounds of the invention are useful as insecticides and arachnicides. They may be applied as solids or in the form of liquid sprays either in conventional type formulations, low volume or as ultra low volume applications, hereinafter referred to as L.V. or U.L.V., respectively.

Solid formulations can be prepared by dissolving the active compound in a solvent, generally a relatively volatile organic solvent, such as xylene, cyclohexanone, a lower alcohol or the like, spraying the solution onto an agitated bed of inert solid carrier, such as attapulgite,

kaolin, talc or diatomaceous earth in granular or finely ground form, and, thereafter, drying the thus prepared formulation. Preparation of wettable powders, which are diluted with water before spraying, usually include the addition of an emulsifier, such as an alkyl aryl sulfonate, alkyl aryl polyglycol ether, and the polyalkylene fatty acid esters. Such formulations usually contain from about to 95% by weight of toxicant and are prepared with finely ground inert carrier.

In general, the liquid sprays can be prepared as concentrates by dissolving the toxicant in an organic solvent, such as xylene, benzene, lower alcohol, fuel oil, or the like, with or without an emusifying agent, and further diluting with either water or an organic diluent, such as deodorized kerosene for application. The concentrates generally contain from about 20% to 95% by weight of toxicant and when diluted for application may contain as little as 0.01% of active material.

The toxicant may also be diluted with a small amount of an essentially non-evaporative solvent, such as the high aromatic solvents (95% or better aromatics), having a flash point above about 125 F., such as Panasol or Socal 44L. The mixture is applied as such at very low rates (i.e., about 1 to 32 fluid ounces per acre).

Advantageously, the compounds of the invention have activity against a wide variety of economically important plant pests. Moreover, they are highly effective as either contact or systemic pesticides and are outstanding for the control of soil insects and provide excellent control of both the larval and adult stages of both insects and arachnids. Additionally, it has been observed that the compounds of the invention are non-phytotoxic at pesticidally effective rates.

The invention will be better understood by referring 35 to the illustrative examples set forth below. These are not to be taken as limitative of the invention. All parts are by Weight unless otherwise stated.

EXAMPLE 1 Preparation of 2-bromo-4-methylcyclohexanone A few drops of bromine are added to a solution of 50 parts of 4-methyl-cyclohexanone, 20 parts (by volume) of glacial acetic acid and 85 parts of water in a suitable reaction vessel. The mixture is then heated to 60 C. until all the bromine is absorbed. An additional 25 parts of bromine are then added to the stirred mixture, keeping the temperature below 60 C. The mixture is next added to ice water, extracted with methylene chloride, and the methylene chloride layer washed with potassium bicarbonate solution and dried. Evaporation of the solvent yields 84.0 parts of 2-bromo-4-methylcyclohexanone as an oil.

EXAMPLE 2 Preparation of 4-methylcycl'ohexane-1,2-dione EXAMPLE 3 Preparation of 6(7)-methyl-2-oxy-5,6,7,8-tetrahydroquinoxaline A mixture of 43.0 parts of 4-methylcyclohexane-1,2- dione, 60.0 parts of glycinamide hydrochloride and 100 parts of water are cooled in ice. 100 parts (by volume) of a 40% sodium hydroxide solution are added and the solution stirred for minutes. It was then acidified and a gummy solid is recovered. The latter is washed with methylene chloride and then triturated with ethanol to yield 4.5 parts of 6(7)-methyl-2-oxy-5,6,7,8-tetrahydroquinoxaline as a white solid, having a melting point equal to 258 C.260 C.

EXAMPLE 4 Preparation of 0,0-diethyl 5,6,7,8-tetrahydro-6(7)- methyI-Z-quinoxalinyl phosphorothioate 4.2 parts of 6(7)-methyl-2-oxy-5,6,7,S-tetrahydroquinoxaline are added to a solution of 4.2 parts of potassium t-butoxide in t-butanol. The mixture is cooled in an ice bath and 3.56 parts of 0,0-diethyl phosphorochloridothioate then added. After 15 minutes, the reaction mixture is poured into a mixture of ice water and methylene chloride. The methylene chloride layer is washed thoroughly with water and dried. The solvent is finally evaporated and the residue chromatographed on alumina to yield 3.30 parts of above-named product as a yellow oil.

Analysis.Calcd. for C H N O PS (percent): C, 49.36; H, 6.64; N, 8.86; S, 10.15; P, 9.80. Found (percent): C, 50.20; H, 6.87; N, 9.97; S, 11.22; P, 10.61.

EXAMPLE 5 Preparation of 2-oxy-5,6,7,8-tetrahydroquinoxaline A solution of 6.0 parts of glycinarnide hydrochloride and 5.0 parts of cyclohexane-l,2-dione in 50 parts of water is cooled in an ice bath and parts of 40% aqueous sodium hydroxide solution are added thereto. After five minutes the solution is heated and vigorously stirred at 40 C. for 1.5 hours. It is then cooled in an ice bath and 30 parts of water are added. Concentrated hydrochloric acid is added until the pH of the solution is about 5. Solid sodium bicarbonate is next added to neutralize the mixture. The solid precipitate is filtered, washed with water, and dried under vacuum to give 5.8 parts (86%) of the desired product, melting point 268 C.- 270 C.

Analysis.-Calcd. for C H N O (percent): C, 63.9; H, 6.70; N, 18.6. Found (percent): C, 63.7; H, 7.00; N, 18.4.

EXAMPLE 6 Preparation of 0,0-dimethyl O-5,6,7,8-tetrahydro- 2-quinoxalinyl phosphorothioate A stirred solution of 5.0 parts of tetramethylene-2 pyrazinone and 3.75 parts of potassium t-butoxide in 100 parts (by volume) of t-butanol is cooled to about C. T o the cooled solution is next added 5.35 parts of 0,0 dimethyl phosphorochloridothioate. Resultant mixture is stirred at room temperature for 15 minutes and then at 40 C. for an additional fifteen minutes. Water is then added and the mixture extracted with methylene chloride. The methylene chloride solution is washed several times with water, dried over magnesium sulfate, and evaporated to yield 5.6 parts of product as a dark oil identified by NMR analysis.

Analysis.Calcd. for C H N O PS (percent): C, 43.79; H, 5.47; P, 11.31. Found (percent): C, 41.81; H, 5.53; P, 10.92.

EXAMPLE 7 Preparation of 0,0-diisopropyl O-5,6,7,8-tetrahydro- 2-quinoxalinyl phosphorothioate Five parts of tetrahydro-2-keto-quinoxa1ine are suspended in 1 00 parts (by volume) of t-butanol containing 5 parts of potassium t-butoxide. The reaction mixture is refluxed for rfifteen minutes, then 5.6 parts of diisopropylphosphorochloridothioate added. The reaction mixture is refluxed until a pH of 7 is attained. Water is then added and the aqueous solution is then extracted with methylene chloride. The methylene chloride solution is separated from the water and dried with magnesium sulfate and upon evaporation of the solvent, the remaining oil is taken .up in petroleum ether and chromatographed on alumina.

6 Elution is eflected first with petroleum ether and then with methylene chloride to yield the above named product on removal of the solvent.

Analysis.Calcd. for C H N O PS (percent): C, 50.90; H, 6.97; N, 8.48; S, 9.72. 'Found (percent): C, 49.09; H, 7.01; N, 8.37; S, 9.46.

EXAMPLE 8 Preparation of diisopropyl 5,6,7,8-tetrahydro- 2-quinoxalinyl phosphate Following the procedure of Example 7 but substituting diisopropyl phosphorochloridate for diisopropyl phosphorochloridothioate, there is obtained the above-named product in good yield.

Analysis.Calcd. for C H N O P (percent): C, 53.51; H, 7.33; N, 8.92; P, 9.87. Found (percent): C, 53.13; H, 7.25; N, 8.75; P, 9.77.

EXAMPLE 9 Preparation of 0,0-diethyl O-5,6,7,8-tetrahydro- 2-quinoxalinyl phosphorothioate 3 parts of tetramethylene-Z-pyrazinone are suspended in 50 parts (by volume) of t-butanol containing 3 parts of potassium t-butoxide. The reaction mixture which was previously flushed with nitrogen is refluxed for one and a half hours. Subsequently, 3 parts of diethyl phosphorochloridothioate are added slowly. Resultant reaction mixture is refluxed for one hour and then diluted with water and extracted with methylene chloride. The organic layer is then separated and evaporated under vacuum. 3.6 parts of a brown oil are collected. The oil is finally washed with cold hexane to obtain 2.8 parts of product.

Analysis.--Calcd. for C H N O PS (percent): C, 47.69; H, 6.29; N, 9.27; S, 10.61; P, 10.25. Found (percent): C, 47.51; H, 6.37; N, 9.07; S, 10.81; P, 10.27.

EXAMPLE 10 Preparation of O-ethyl O-methyl O'-5,6,7,8-tetrahydro- 2-quinoxalinyl phosphorothioate 5 parts of tetrahydro-Z-keto-quinoxaline are suspended in parts (by volume) of t-butanol containing 5 parts of potassium t-butoxide. The reaction is refluxed for onehalf hour, then 5 parts of O-ethyl, O-methyl phosphorochloridothioate are added. The reaction mixture is stirred first at room temperature for one half hour, then at reflux temperature for 3 hours and left overnight at room temperature. Water is added and the mixture extracted with methylene chloride, dried, evaporated and chromatographed to obtain 4.6 parts of product.

Analysis.Calcd. for C H N O PS (percent): C, 45.83; H, 5.90; N, 9.72; P, 10.76. Found (percent): C, 45.65; H, 6.13; N, 9.97; P, 10.53.

EXAMPLE 11 Preparation of N,N-dimethyl-O-ethyl O5,6,7,8tetrahydro-2-quinoxalinyl phosphoroamidothioate 5.0 parts of tetrahydro-Z-keto-quinoxaline and 3.8 parts of potassium t-butoxide are dissolved in about 100 parts (by volume) of dimethylsulfoxide and cooled to 10 C. 6.3 parts of O-ethyl-N-dimethyl phosphorochloridoamidate are added to the mixture and held under agitation at room temperature for one-half hour. It is then extracted with methylene chloride, and the organic layer washed with water and dried to yield 7.5 parts of a yellow oil.

Analysis.-Calcd. for C H PN S0 (percent): C, 47.9; H, 6.68; N; 13.97; S, 1063; P, 10.29. Found (percent): C, 48.06; H, 6.83; N, 14.04; S, 10.62; -P, 10.25.

i EXAMPLE 12 Preparation of O-ethyl-O-S,6,7,8-tetrahydro-6(7)- methyl-Z-quinoxalinyl phenylphosphonothioate To a stirred solution of 5 parts of tetramethylene-Z- pyrazinone and 3.8 parts of potassium t-butoxide in 150 parts (by volume) of dimethylsulfoxide at about 10 C. are added 3.8 parts of O-ethyl phenylphosphonochloridothioate. The mixture is worked up, as in Example 11, to yield 5.5 parts of a yellow oil.

Analysis.Calcd. for C H PN SO (percent): C, 57.5; H, 5.72; N, 8.39; S, 9.58; P, 9.27. Found (percent): C, 57.72; H, 5.68 N, 8.15 S, 9.82 P, 9.26.

EXAMPLE 13 Preparation of O,S-dimethyl O-5,6,7,8-tetrahydro-2- quinoxalinyl phosphorodithioate parts of 5,6,7,8-tetrahydro-2-keto-quinoxaline are suspended in 100 parts (by volume) of t-butanol containing 5 parts potassium t-butoxide. To this mixture, after stirring at reflux for /2 hour, are added five parts of 0,8- dimethyl phosphorochloridodithioate. The reaction mixture is stirred at room temperature for sixteen hours and then refluxed for one-half hour. Then water is added and the reaction mixture extracted with methylene chloride. The methylene chloride layer is dried over magnesium sulfate and evaporated to dryness. The dark oil is taken up in petroleum ether and the formed solids are filtered and the filtrate chromatographed on alumina. Elution with petroleum ether and methylene chloride yields 2.5 parts of pure product, analyzing in percent as: Calcd. for

io is z z a (percent): C, 41.36; H, 5.17; N, 9.65; S, 22.12; P, 10.68. Found (percent): C, 40.96; H, 5.35; N, 8.17; S, 18.26; P, 8.93.

EXAMPLE 14 Preparation of O-ethyl-O-S,6,7,8-tetrahydro-2- quinoxalinyl ethanephosphonate To a stirred suspension of 5 parts of tetramethylene-Z- pyrazinone and 3.8 parts of potassium t-butoxide in 150 parts (by volume) of t-butanol which had been stirred for one hour at room temperature, are added 5.23 parts of ethyl ethanephosphonochloridate. Reaction occurred immediately and the mixture is worked up and then washed with cold n-hexane yielding 6.5 parts of yellow oil. This is taken up in hot hexane, treated with a small amount of alumina, then with charcoal, filtered while still hot, and concentrated leaving 5.2 parts of product whose index of refraction (n is 1.5128 and analyzing as: Calcd. for C H PN O (percent): C, 53.3; H, 7.08; N, 10.36; P, 11.44. Found (percent): C, 52.96; H, 6.83; N, 10.22; P, 11.29.

EXAMPLE 15 Preparation of S,S-dimethyl O-5,6,7,8-tetrahydro-2- quinoxalinyl phosphorodithioate 5.0 parts of tetramethylene-2-pyrazinone and 3.75 parts of potassium t-butoxide in 250 parts (by volume) of t-butanol are stirred at room temperature for two hours. 5.9 parts of S,S-dimethyl phosphorochloridothioate are then added and the mixture immediately treated with methylene chloride, washed with water and dried to yield 8.3 parts of yellow oil. The latter is washed with ice-cold hexane, taken up in hot benzene-hexane mixture, treated with charcoal, filtered and concentrated to yield 5.5 parts of an orange oil.

Analysis.-Calcd. for C H PN S O (percent): C, 41.4; H, 5.21; N, 9.65; S, 22.05; P, 10.65. Found (percent): C, 41.15; H, 5.20 N, 9.42; S, 22.12; P, 10.59.

EXAMPLE 16 Preparation of O-isopropyl O-methyl-O-5,6,7,8-tetrahydro-2-quinoxalinyl phosphorothioate 2.5 parts of potassium t-butoxide are dissolved in 100 parts (by volume) of t-butyl alcohol and added to a stirred solution of 3.0 parts of tetramethylene-Z-pyrazinone in t-butanol. The mixture is stirred until a clear brown solution is formed in about 15 minutes at 45 C. When mixture has been cooled to about 40 C., 3.7 parts of O-isopropyl O-methyl phosphorochloridothioate in tbutanol are added all at once. This mixture is partitioned between parts of water and 100 parts (by volume) of methylene chloride.

The water layer is extracted with 50 parts (by volume) of methylene chloride, and the combined layers washed with 50 parts of water, followed by aqueous 1% sodium bicarbonate and then again with water. After drying over sodium sulfate and filtered to remove solvent, 4.5 parts of brown oil are obtained.

Analysis.Calcd. for PN SO C H (percent): C, 47.67; H, 6.33; N, 9.27; P, 10.25; S, 10.61. Found (percent): C, 47.31; H, 6.70 N, 10.21; P, 10.26; S, 10.88.

EXAMPLE 17 Preparation of diethyl 5,6,7,8-tetrahydro-2-quinoxalinyl phosphate 10 parts of tetramethylene-Z-pyrazinone are dissolved in 300 parts (by volume) of t-butanol containing 10 parts of potassium t-butoxide and reacted with 10 parts of diethyl phosphorchloridate. The mixture is stirred for two hours, then refluxed for 20 minutes and allowed to cool. Water is added to dissolve the resultant solid and the solution is extracted therefrom with methylene chloride. The methylene chloride layer is separated from the water, dried over magnesium sulfate and concentrated to obtain the desired product which analyzes as: Calcd. for C H N O P (percent): C, 50.37; H, 6.64; N, 9.79; P, 10.83. Found (percent): C, 50.50; H, 6.60; N, 9.90; P, 10.70.

EXAMPLE 18 Preparation of 0,0-dipropyl 0-5,6,7,8-tetrahydroquinoxalinyl phosphorothioate 5 parts of tetramethylene-Z-pyrazinone are suspended in 100 parts of t-butanol containing 5 parts of potassium t-butoxide. The reaction mixture is refluxed for one-half hour. 5 parts of di-n-propyl phosphorochloridothioate are then added. Resultant reaction mixture is refluxed for another two hours, water then added and the solution extracted with methylene chloride. The methylene chloride solution is dried over magnesium sulfate and evaporated to dryness. The oil which remains is taken up in petroleum ether. The solution is filtered to remove starting material and the petroleum ether solution chromatographed on alumina. Elution of the above solution with methylene chloride and subsequent removal of solvent yields the desired product which analyzes as: Calcd. for C H N O PS (percent): C, 50.90; H, 6.97; N, 8.48; S, 9.72; P, 9.39. Found (percent): C, 50.80; H, 7.00; N, 8.37; S, 9.65; P, 9.19.

EXAMPLE 19 The insecticidal activity of typical compounds of the invention is demonstrated by the following tests wherein graded levels of toxicant are used for controlling a variety of insect species. Test procedures as well as the results obtained are set forth below:

Bean aphidAphis fabae Scopoli Compounds are tested as 0.1%, 0.01% and 0.001% solutions or suspensions in 65% acetone-35 water. Twoinch fiber pots, each containing a nasturtium plant about two inches high and infested with about aphids two days earlier are sprayed with the test solutions so as to give complete coverage of the aphids and the plants. The sprayed plants are laid on their sides on white enamel trays which have had the edges coated with oil as a bar rier. Mortality estimates are made after holding for two days at 70 F., and 50% RH.

Activity reported in Table I as percent kill of insects.

Aphids, percent Structure (CHa)zCHO-1"O /N 100 100 100 Southern arm worm-Proden'a eridania Crame y l r) The dishes are covered and held at 80 F., and 60% The solutlons from the aphid test above are also used for this test Sieva lima bean primary leaves are dipped R.H. After 2 days, mortality counts and estunates of the for three seconds in the test solution and set in a hood amount of feedmg are madeon a screen to dry. When dry, each leaf is placed in a 4- Activity is reported in Table II as percent kill obtained inch petri dish which has a moist filter paper in the bottom with each level of toxicant with ten third-in-star armyworrn larvae about long.

TABLE 11 Southern armyworm, percent Structure 1 01 001 I N (G H 0) I -O 100 100 90 s II N carom-of 100 100 u N carom-0 100 100 II N 11-0311 0 zP-0r 100 o 0113s s N CzH50\(") N CzH5O\fi N /POF l 100 100 0 13 14 Confused flour beetle (TC)Triblium confusum To MB G 0, Jacquelm duVal structure 1% 1%, 1%

Compounds are formulated as 1% dusts on talc by 0 100 100 100 admixing toxicant and talc, wetting with acetone and (02H grinding with a mortar and pestle until dry. 125 mg. of 5 5 this 1% dust are then blown into the top of a dust settling tower. The dust is allowed to settle on four-inch petri \N/ dishes for two minutes, giving a deposit of approximately 87 mg./sq. foot of the 1% dust. The dishes are removed N 30 and 25 adult confused flour beetles are added immediately. 10 (i-C H O)2PO- The dishes are held for three days at 80 F. and 60% RH, following which mortality counts are made. \N/ Large milkweed bug (MB)-Onc0peltus fasciatus Dallas S 20 The 1% dusts described above are used 1n this test. [l %N 5 50 The 1% dust is sprinkled evenly over the glass bottom (IC3HYO)ZP O of a seven-inch diameter cage, giving a deposit of approximately 94 mg./sq. foot of the 1% dust. Water is supplied in a bottle with a cotton wick, twenty adult bugs are added and a screen cover placed on the top. Mortality N 100 100 50 counts are made after holding for three days at 80 F. ll and 60% RH.

German cockroach (GC)Blattella germanica (Linnaeus) The procedure is the same as for the large milkweed bug test, except that in this test only aduct males are used.

'11 'n cts Data are report.ed m Table In as percent k1 of 1 Se I11 addition to the above tests, aqueous/acetone soluat the level of toxicant employed.

tions containing etiher 100 p.p.m. or 0.1% of a test com- TABLE III I pound are applied to leaves of cotton plants. The leaves Structure are permitted to dry, placed in petri dishes on a moist 100 100 100 filter paper and infested with Lygus lineolaris, Anthono- II mu-s grandis or Heliothis virescens. The petri dishes are (OzI-ROhP-O D then placed 1n a constant temperature room held at 80 F. \N/ and RH. for two days. After two days, mortality 40 counts are made and percent kill of insects recorded. H N Further, it has been found that the compounds of the (CHBO)2PO 100 100 100 present invention exhibit residual activity against the l above-mentioned cotton pests. \N The results are tabularized in Table IV below.

TABLE IV Anthon- Lygus, omus, Heliothis, Structure p.p.m. 100 p.p.m.100 p.p.m.100

s N I (C2Il50)2 D s 100 100 II N (CHaO)zP0 0 100 90 100 II N 2 s )2 O v, /N\ C2115 021150 s so 100 100 To show the eifectiveness against common malaria mosquito, Anopheles quadrimaculatus, test compounds are prepared as 10 p.p.m. and 1.0 p.p.m. solutions in acetone and coated on a hard surface accessible to contact by 4- to 5-day old mosquitoes of mixed sexes. A sugar solution is provided as food for the mosquitoes which are caged for 24 hours in such manner as to permit exposure of the mosquitoes to the treated surface. After the 24 hour period, mortality counts are made and the results recorded.

Test results are tabulated in Table V below.

TABLE V Mosquito, Adult Structure 10 p.p.m. 1

100 40 II N (C2H5O)2PO 100 70 II N (CH O)2PO II N (C2H50)2P-O-r C2H5O-S 100 100 N P-O \II N /PO 01130 N P-O N 100 0 (C2H O) PO- J CH N To demonstrate the eifectiveness against the hou efly. Musca domestica Linnaeus, groups of '25 adult female housefiies are placed in wide-mouth pint mason jars, and covered with a screen cap. The test compounds are formulated as :an emulsion containing 1000 p.p.m. of test materials, an emulsifier, acetone, and water. This emulsion is diluted with 10% sugar solution, giving a concentration of 50, 5 or 0.5 p.p.m. The solution is placed so that the flies can feed on it through the screen. Mortality counts are made after two days at 80 F.

Results obtained are reported in Table VI below.

TABLE VI Fly,p.p.m.

5 Structure 50 5 .5

s II N (C2H O)zPO 100 10c 20 II N (CHaO)2P-O 100 100 24 II N o2H.o)21 o- 100 100 100 II N (iC H O)zPO- 100 100 9a I] N i-o.H 0)2P-o- 100 88 12 II N (n-O H O)2PO- 100 100 0 N C2H5O\fi N P-0- 100 100 so II N (CH3S)zP0 100 12 0 N 01ns\ N /PO-// 100 o CH30 L \N/ CzHaO\$l) N CzHg,

i o 100 0 Q N s II N 2H50)2P0( 100 100 0 CH3 K II N s)2CHO-PO 100 100 56 7 CHaO EXAMPLE 20 The systemic activity of the compounds of the invention is demonstrated by the following tests.

17 The compound to be tested is formulated as an emulsion containing test material, an emulsifier, acetone, and water. This is diluted with water to give 100, 10 or 1 ppm. of toxicant in test. A sieva lima bean plant with only the primary leaves unfolded is cut off just above soil level Sieva lima bean plants with primary leaves three to four inches long are infested with about 100 adult mites 5 and Inserted a bottle of test emulslon and held m per leaf four hours before use in this test. The mite and place by a b1t of cotton wrapped around the stem. The bottle is then placed in a ventilated box with the leaves egg Infested plants i dlpped for three Seconds 111 t ndi t id th b h h t any ibl fumes 0.01 or 0.001% solutions of test compound, and the plants from the compound will be drawn out the end of the set in the hood to dry. They are held for two days at gfi t? i f a to g the telst ii g 80 F., 60% R.H., and the adult mite mortality estimated 2 er figg i i g gg gf 2; 3; fiffi z on one leaf under a stereoscopic microscope. The other estimates are made and one l f from each Plant is leaf is left on the plant an additional five days and then placed on a moist filter paper in the bottom of a petri dish. 15 eXa d at 1 X power to es mate the kill of eggs and Ten third-instar southern armyworm larvae are added to each dish and mortality counts are made after holding another three days at 80 F. and 60% RH.

TABLE VII Systemlcs Southern army- Mites, p.p.m. worm,p.p.m.

Structure 100 10 1 100 10 1 s 100 100 0 100 70 0 n N a l )2 s N 100 100 0 100 100 0 amon -of 1] (CzH)2P AK 0.1150 s 100 as 0 100 100 o \{LOAEIRQ C2115 s 90 0 100 50 II N\ C2H50)2P-O s 100 64 100 II N (CH3)2CHOPO EXAMPLE 21 of newly-hatched nymphs, giving a measure of ovicidal Arachnicidal activity of the compounds of the invention is demonstratedlagainst the two-spotted spider mite, Tetranychus urticae (Koch).

and residual action, respectively. Solutions are made in 65% acetone-35% watervand the results are reported in,

tabular form in Table VIII below.

TABLE vnr Mites, percent Structure .1 .01 .001

i N 100 100 87 airshow-% Q fi N 100 100 100 (CHaO)2P-O( I) a N 100 100 100 2H5 )z -O O2H50\fi N 100 100 0 PO/ shN N 1-o3H 0 21 -0- N l 100 o o l N (i-CaH O)zP-Of l s N 100 o o (n-Ca 1 )2 0 Q we) onto N 100 100 o ornsnr-o 3 \N CHaS\fi N 100 o o /PO/ CHaO CzH5O\h) N 100 100 100 /PO CzH5 02H60\fi N 100 100 60 20 EXAMPLE 22 Larvicidal activity of the compounds of the invention is shown in the following tests against the larvae of the malaria mosquito.

Common malaria mosquito-Anopheles quadrimaculatus Say Larvicide test Groups of 25 larvae of the common malaria mosquito are placed in a 50 ml. beaker containing 25 ml. of water. The test compound is formulated as an emulsion containing .4 or .1 ppm. of test material, emulsifier, acetone, and Water. The larvae in 25 m1. of Water are added and mortality counts are made after 24 hours at F. and recorded in Table 1X.

TABLE IX Mosquito, Larvae, Structure p.p.m..4 p.p.m. .1

i N 100 (CZH5O)2PO-[/ n s 100 100 on ohi -o /N o 100 0 ozn ohi of n s 100 20 (n-O H O)z1 -O-[ n C2H50\fi N 100 100 1 -0 CHaO I) \Lo /N CHsO t CzHs0\(fi N 100 0 P--O CzHu I] OZHEO s 100 so i -o( Q l l i N 100 100 (whom-0f EXAMPLE 23 into the soil at the equivalent of 50 toll) pounds per Soil insecticidal activity is demonstrated by the follow- 6'inch acre The Soil is sub'sampled mm wide mouth bottles and ten 6- to 8-day old rootworm or wireworm mg tests usmg the false wireworms, Eleodes suturals Say and the Southern corn rootworm, Diabrotica undecimizi g giiig 9 2 335322 32 3 1S g g g gb punctata how ardi Barber. y ays a 5 The compound is formulated as a dust and incorporated and recorded m Table X below TABLE X Rootwonns, Wireworms, lbs/acre lbs/acre Structure 10 50 10 s H N (CzH5O)2P-OT 100 100 100 100 \N s H N (CH OhP-Of 100 100 100 \N O II N (C2H50)zP-0 100 85 100 100 I N 1-c H 0 2 -0- 100 65 o S II N (CH )zCHO-P-O 100 100 100 23 We claim: 1. A method 101' controlling insects and arachnids which comprises: applying thereto a plastically effective amount of a compound of the formula:

wherein X is a member selected from the group consisting of sulfur and oxygen; R and R are each lower alkyl, lower alkoxy, lower thioalkyl, phenyl, halophenyl, benzyl or -NR R R is hydrogen or lower alkyl; and R and R are each selected from the group consisting of hydrogen and lower alkyl.

5. The method according to claim 1 in which the compound is: diisopropyl 5,6,7,8 tetrahydro-Z-quinoxalinyl phosphate.

6. The method according to claim 1 in which the compound is: 0,0-diethyl O-5,-6,7,8-tetrahydro-2-quinoxalinyl phosphorothioate.

7. The method according to claim 1 in which the compound is: O-ethyl O-methyl O 5,6,7,8 tetrahydro-Z- quinoxalinyl phosphorothioate.

8. The method according to claim 1 in which the compound is: O-isopropyl O-methyl O-5,6,7,'8-tetrahydro-2- quinoxalinyl phosphorothioate.

9. A method of controlling insects and arachnids which comprises applying to their habitat a pesticidally effective amount of a compound of the formula of claim 1.

10. A method of protecting crops from insect and arachnid attack which comprises applying to said crops or to soil in which they are planted, a pesticidally effective amount of a compound of the formula of claim 1.

References Cited UNITED STATES PATENTS 3,150,149 9/1964 Uhlenbroek et a1. 260250 ALBERT T. MEYERS, Primary Examiner L. SCHENKMAN, Assistant Examiner "U wee STATES PATENT GFFICE QERTEFICATE G QJUREEETIGN Patent No. 5,577 ,556 j Dated May 5, 1971 Invent0r(s) Bernard Miller an Tamara Helen Mladineo Gund It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 2, line 26, "conomical" shculd --econemical.

Column 3, line 2, "helegenrising sheuld reacl a1.ogenat1ng--.

Celumn 5, line 50 pohsphorochloridothioete should read ----pnoepino2.-ecsnloridothioa'ce--o Colmn 7', line 355 ethyl-O-Ei" should read -e*i:'nyl 0-5".

Cclumn 8, line 2% phosphcrchlor'idece mould read "prwepnorochloridate--.

I, eighth line down, 1(3 should read --lOO--w Column 13, line '26, "aduct sheuld reae -ao'iul*b.

001mm 15, line 35, C H O-S shculc'; partially read a e-1 o s" U FORM 90-1959 H9691 QscoMM-oc wave-ps9 

